CHAPTER 3 ASTM DISTILLATION, TRUE BOILING POINT DISTILLATION, AND EQUILIBRIUM FLASH VAPORIZATION RELATIONSHIPS FOR PETROLEUM FRACTIONS 3-0 INTRODUCTION ASTM and true boiling poi tillations are used to define the volatility characteristics of petroleum fractions and other complex mixtures Both are batch distllations which differ mainly in the degree of fractionation obtained during the distillation. ‘Atmospheric ASTM distillations are run in an Engler flask. No packing is employed, and reflux results only from heat losses through the neck of the flask. ASTM distillations are more widely used than TBP distillations because the former are simpler, less expensive, require Jess sample, and require only approximately one-tenth as much time. Furthermore, ASTM distillations are standardized, whereas TBP distillations vary appreci- ably in procedure and apparatus. ASTM distillation methods in use today are: ASTM Method D86: This method is used for the dis- tillation of motor gasolines, aviation gasolines, aviation turbine fuels, naphthas, kerosines, gas oils, distillate fuel oils, and similar petroleum products. It is carried out at atmospheric pressure. An exposed thermometer is used, and temperatures are reported without stem corrections. ASTM Method D216: This method is used for the di tillation of natural gasoline and is performed at atmo- spheric pressure. ASTM Method D1160: This method is used for heavy petroleum products which can be vaporized partially or completely at a maximum liquid temperature of 750 F at absolute pressures down to 1 mm Hg and condensed as liquids at the pressure of the test. Itis carried out at pressures between 1 mm Hg and 760 mm Hg, absolute. ‘Temperatures are measured with a thermocouple. ASTM Method D2887: Simulated distillation (SD) by gas chromatography appears to be the most simple, reproducible, and consistent method to describe the boiling range of a hydrocarbon fraction unambiguously This method is applicable to all petroleum fractions with a final boiling point of 1000 F or less. The method is also limited to samples having a boiling range of at least 100 F. Figure 3-0.1 shows a typical relation be- tween ASTM D86 and ASTM D2887 distillations for a naphtha fraction. It should be noted that ASTM D86 distillations are plotted in volume percent while simulated distillations are plotted in weight percent. 1987 (TBP) analytical dis- In ASTM distilations there may be a residue left in the distillation equipment as well as a difference be- tween the volume of the original charge and the sum of the distillate and residue. This difference is usually termed “Joss” and is generally thought of as volatile components of the charge which have not been recon- densed. For preparation of an ASTM distillation for conversion to a TBP or equilibrium flash vaporization (EFV), the percent distilled at the reported tempera~ ture is the sum of the distillate collected and the loss. When heated sufficiently hot, petroleum fractions undergo thermal cracking. Although’ a function of chemical composition, the amount and severity of ther- mal cracking increases with increasing boiling point, contact time, pressure and temperature. Previous edi- tions of this chapter included a correction for eracking for observed ASTM D86 temperatures above 475 F. In this revision, no correction for cracking is included. 800 700 * 600 500 400 TEMPERATURE 300 200 0 2 40 60 80 100 PERCENT VAPORIZED Soutce: Edniser and Pollock, Chem. Eng. Progr, 4495 (1948) Figure 3-0.1—Typical ASTM D86 and Simulated Distillation Curves for a Naptha Petroleum Fraction at3-0 ‘TBP distillation are performed in columns with 15 t0 100 theoretical plates at relatively high reflux ratios (ie., 5to 1 or greater). The high degree of fractionation in these distillation gives accurate component distribu- tions for mixtures. The lack of a standardized apparatus ‘and operational procedure is a disadvantage, but the variations between various laboratories are small be- cause a close approach to perfect component separation is usually achieved. The EFV curve is also a plot of temperature against percent by volume of liquid distilled, with the total ‘vapor in equilibrium with the unvaporized liquid at a ‘constant pressure. Each point on the EFV curve repre- sents a separate equilibrium experiment. The number of equilibrium experiments needed to define all por- tions of the EFV curve varies with the shape of the curve. Normally, at least five such experiments are re~ quired. Figure 3-0.2 also shows the EFV curves of a naphtha-kerosine blend at atmospheric and several superatmospheric pressures. ‘The tedious procedures necessary to obtain experi- mental EFV data have given impetus to the develop- ment of correlations for predicting EFV data from the analytical ASTM and TBP disilations. Both empirical and theoretical prediction methods have been devel- oped ‘Additional figures are presented for predicting the properties of the products of an equilibrium flash vaporization. Specifically, Figure 3B4.1 should be used to estimate the overhead product ASTM distillation curve, Figure 3B4.2 to estimate the bottoms product distillation curve, and igure 3B4.3 to estimate the APT eravities of both products Users are emphatically cautioned against relying heav- ily on results obtained from these correlations. Because of a lack of standardization and other inherent inade- ‘quacies in the methods, the existing ASTM, TBP, and EFV data are not sufficiently precise or consistent to develop good correlations. ‘The correlations ofthis chapter were developed using data for hydrocarbon stocks and fractions which in- cluded many components and exhibited smooth dis- fillation curves. The correlations do not apply to mix- tures of few compounds with widely different boiling points. Some published methods of predicting EFV data from the analytical ASTM and TBP distillations are given in references 7 through 9, 21 through 28, 39, and 40. These methods are usually based on dividing the complex mixtures into a series of narrow-boiling cuts or fractions, each characterized by its mean or average boiling point. Each cut is viewed as representing an 32 individual or pseudo component in a simulated mult component mixture. ‘A fecent approach to characterizing wide boiling range petroleum fractions is to use the method of continuous thermodynamics (12, 13, 77). This method provides a continuous distribution function for the Property desired. While such methods are still in the developmental stages, they show promise for carrying ‘out phase equilibrium calculations of undefined, multi- component mixtures. ‘A schematic diagram of the interconversion proce- dures is shown in Figure 3-0.3. Correlations are sum- marized in Table 3-0.4, Correlations in this chapter are empirical in nature and are arranged according to the various paits between ASTM, TBP, SD, and EFV relations. Section 3A1 ASTM-TBP (Atmospheric) Section 32. ASTM-TBP (Subatmospheric) Section 3A3 ASTM-SD (Atmospheric) Section 3B1 ASTM-EFV (Atmospheric) Figure 3-0.2—ASTM, True Boiling Point, anc Equilibrium Flash Vaporization Distillation Curves for a ‘Naphtha-Kerosine Blend 1987Section 382 ASTM-EFV (Subatmospheric) Section 383 ASTM-EFV (Superatmospheric) Section 385 TBP-EFV — (Subatmospheric) ‘TBP distillation data obtained at one pressure may be converted to another pressure by Procedure 344.1 ASTM distillation data may be similarly converted (as described in ASTM Method D1160) but with somewhat reduced reliability. The preferred procedure for con- verting ASTM distillation data taken at one pressure to that at another pressure is to obtain the corresponding ‘TBP data, convert these by Procedure 3A4-1, and then reconvert to ASTM distillation data. The procedure is ‘outlined for 10 mm Hg to 1 atmosphere in Table 3-0.4 Lamb and Sitar (45) theoretically and experimentally analyzed the conversion of distillation data from one pressure to another. They presented a modified Cox chart for petroleum fractions ASTM apparatus and procedures have changed over the years. TBP apparatus and procedures have never been standardized. Reproducibilities of ASTM and 30 ‘TBP distillations are a function of the distillation curve slope, and differences often become as high as 30 F. In addition, a large portion of the experimental data used to construct the correlations was obtained by non- standard test methods. Equilibrium flash data, while probably more repro- ducible than ASTM and TBP data, were obtained using different types of apparatus and many variations in pro- cedure. Procedure 3C1.1 is a computer method for flash cal- culations and estimation of equilibrium K-Values for petroleum fractions using a modified Soave-Redlich- Kwong (71) equation of state. This procedure is be- lieved to be the most accurate of the methods presented. Nore: A report which documents the basis upon which the original material in this chapter was selected has been pub- lished by the American Petroleum Institute as Documentation Report No. 3-66 and No. 2,3-86. Procedure 3D1.1 is docu- ‘mented in Documentation Report No. 2-81 Table 3-0.4—Summary of Correlations for Handling Distillation Data Data Available Pressure, ‘Type ‘mm Hg ‘Type ASTM D2887 (SD) 160 ASTM D86 ‘ASTM D6 760 TBP ‘ASTM D1160 10 ‘TBP. ASTM D1160 10 TEP ASTM D116 10 ASTM DB6, ‘ASTM 86 160 EFV ‘ASTM D1160 10 EFV EFV 160 EFV TBP 10 TBP ‘TBP 7160 EFV TEP 10 EFV EFV Subatmo- —- EFV spheric ASTM D2887 (SD) 160 TBP. ASTM D286? (SD) 760 EFV ASTM D1160 1 ‘TeP. ASTM D160. 1 ASTM D86 ‘ASTM D1160. 100 TBP. ‘ASTM D1160 100 ASTM D86 Conversion Data Desired Reet Pressure, Steps in ‘mm Hg Fig. 30.3 760 3 160 1 10 2 160 24 160 241 760 A 10 6 Superatmo. 7 spheric 760 4 760 fs 10 8 (Steps 5, 4 preferred if ASTM 86 available) Other Subatmo- 4 spheric 160 3,1 760 3s 160 4.24 760 4,204,1 760 424 760 aa Note: All ASTM D86 temperatures at 760 mm Hg are observed values. 1987 3830 ‘ASTM 02687 SIMULATED eFV DISTILLATION (Gas CHRON) Superatmosphoric | 3 lt 7 ‘ASTM D86 eFV 760 men 5 760 mm 4 a Ter 760 mm 4 4 4 4 TeP rt TBP 8 eFV eFV 4 4 Subatmospheric 10mm 10mm Subatmosphoric 2 6 ASTM 01160 ASTM 01160 4 Subatmospheric tomm STEP PROCEDURE 7 aAta 2 3A21 4 3 3A34 4 BAA 5 3814 ASTM 01160 6 382.1, 9822 "aported 7 383.1 a 2 oe 8 385.1, 386. Figure 3-0.3—Interconversion of Varlous Distilations a4 19873At4 PROCEDURE 3A1.1 INTERCONVERSION OF ASTM D8§-TBP DISTILLATION CURVES AT ‘ATMOSPHERIC PRESSURE Discussion ‘The following equations are used to interconvert ASTM D86 and atmospheric TBP dis- tillation data, ‘TBP ~a(ASTM D86)* Galt) ASTM D86= a (TBP) G@a1a2) Where: ¢ a,b constants varying with percent of liquid sample distilled as given below: Volume % distilled a > 0 09167 1.0019 10 oso 1.0900 30 0.7429 1.04025 50 0.8920 1.0176 0 o.g70s 1.0226 30 0.9490 1.0110 95 0.8008 1.0385 TBI true boiling point temperatures at 0, 10, 30, 50, 70, 90, and 95 volume percent distilled, in degrees Rankine ASTM D86= observed ASTM D86 temperatures at corresponding volume percent dis- tiled, in degrees Rankine Equations 3A1.1-1 and 3A1.1-2 are also shown in Figure 31.2. Procedure ‘Use equation (3A1.1-1) or equation (3A1.1-2) according to the type of distillation desired, or use Figure 31.2 for appropriate conversion. 1987 3536 COMMENTS ON PROCEDURE 3A1.1 Purpose ‘The purpose of this procedure is o predict an atmospheric TBP distillation from an ASTM 186 distillation or to predict ASTM D86 data from an atmospheric TBP distillation. This procedure is intended for both desk and computer use Limitations AAs discussed in the introduction, occasional severe ertors may arise from the use of this procedure especially at the initial point. Furthermore, it should not be used for converting ‘ASTM to TBP data for use with Procedure 3C1.1 since the flash calculations of Procedure 3CLA1 are highly sensitive to slight inaccuracies in the TBP curve. ‘This procedure should not be used outside the following temperature ranges: ASTM D86 TBP. ‘Temperature ‘Temperature Volume % Distilled Range, F Range, F 0 73-599 = 50-616 10 97-583 s1-S61 30 119-596 97-550 50 138-608 135-608 7 151-621 153-626 %0 166-647 181-662 95 162-750 163-794 Reliability Differences between the estimated and experimental TBP and ASTM D86 temperatures are as given below at various volume % distilled points. ‘Volume % Distilled Average Deviation, F 0 21 10 m1 30 16 50 61 0 66 0 79 95 uw Deviations are valid when stating with either an ASTM or TBP distillation and converting to the other. Seventy-eight sets of data were used in developing this procedure over the entire range of applicability Special Comments This procedure gives lower values for the temperature difference between the TBP 50% point and the ASTM D86 50% points at all temperatures above about 550 F than do other established methods such as those of Edmister and Pollock (32) used in previous editions and Edmister and Okamoto (29, 30) used by several large petroleum companies. As essentially no data are available above an ASTM 50% temperature of 650 F, results above this tempera ture are not reliable using any of the methods available, As the data base is sparse, the use of different data to derive the relationships may change the results substantially This method is the best that can be derived from all data availabe to the developers. Users ‘may wish to check it with proprietary data before using it for design purposes. Literature Source ‘This procedure was developed by M. R. Riazi, The Pennsylvania State University, Univer- sity Park, Pa., private communication (1986), Example Estimate the atmospheric TBP distillation curve of a petroleum fractio ing ASTM D&6 distillation temperatures:1987 Volume percent distilled 1 3 «50-1 s ASTM D86 temperature, F 350380404433 469 4D Using equation (ZAL.1-1) at each point, e-g., ‘TBP @ 10% point = 0.5277(350 + 460)!" =781R =301F When TBP temperatures at other points on the curve are estimated similarly, the complete predicted ‘TBP curve is as follows: Volume percent distilled : 0 0 590 1 9% 95 TBP temperature, Fees 32 STL 409474502 ‘The corresponding experimental TBP temperatures are: Experimental TBP temperature, F 312 358 40244286899 Now, obtain the ASTM D86 temperatures from the above experimental TBP temperatures using Figure 31.2 ‘The ASTM D86 temperatures obtained from Figure 3A12 using the expetimental "TBP temperatures are as follows ‘Volume percent distilled... 10 30 50 mM] Ms ASTM D86 temperature, F MS 367 400430464475 379005 ro 85044 E 50 FIGURE 3A1.2 8004 : ASTM D86-TRUE BOILING POINT f 100 DISTILLATION CONVERSION coor L450 AT ATMOSPHERIC PRESSURE 700-4 E TECHNICAL DATA BOOK 4 200 ip WUNE 1986 a Approved: TED F250 7 600-4 w E300 yy 550-4 E z Lo F350 © a 500 4 = 4 ui wi a « 4 F400 a = 5 450 = mi & a 2 < F450 F a & 4004 E i & a 500 O & 3505 = - = E 550 300 4 F580 & & E 600 © 2604 E ft 650 200 4 E 700 1504 E 750 100 4 F 800 504 © 850 oF -so-4 -1004 38 1987BA2.1 8 8 ‘TeP TEMPERATURE DIFFERENCE, C 8g & » FIGURE 302.1 SUBATMOSPHERIC. ASTM CISTILLATION “ND TRUE eoLING FONT. » i Satu Wao Pease bercrence 2 == ASTM D 1160 TEMPERATURE DIFFERENCE, C 1987 39A241 COMMENTS ON FIGURE 342.1 Purpose “This figure relates ASTM D1160 and TBP distillation data at 10 mm Hg absolute pressure. Reliability [No quantitative evaluation of the correlation could be made because of lack of data. The original reference indicates that temperatures from this method will be within 25 F of the experimental values. Special Comment ‘The ASTM D1160 and TBP 50-percent points at 10 mm Hg are assumed to be equ Literature Source ‘Adapted from Edmister and Okamoto, Petrol. Refiner 38 [9] 271 (1959). Example Estimate the TBP curve at 10 mm Hg for a petroleum fraction having the following ASTM D160 distillation temperatures at 10 mm Hy: Volume percent distilled 1 30 0 ASTM D1160 temperature, F 300 400475580650 Firs, from Figure 3A2.1, find the temperature differences for each segment of the TBP curve at 10 mm Hg: 10. mm Hg 10 mum Hg TBP ASTM D160 ‘Temperature “Temperature Difference Segment of Curve Difference (fom Fig. 342.1) (Volume Percent) (Fahrenheit Degrees) (Fahrenheit Degrees) 101030 100 106 30 t0 50 75 82 3010 70 5 i 7010 9 100 100 ‘The TBP temperatures are then calculated. The ASTM D1160 and TBP éistillation ‘S0-percent temperatures are assumed to be equal at 10 mm Hg absolute pressure. Here, the ‘S0-percent temperature is 475 F: 10-percent temperature = 393 ~ 106 = 287 F 70-percent temperature = 475-+ 75 = 550 F 30-percent temperature = 475 — 82= 303 F 90-percent temperature = 550+ 100 = 650 F 310 1987303.1 PROCEDURE 343.1 CONVERSION OF SIMULATED DISTILLATION (ASTM 02887) TO ASTM D86 DISTILLATION ‘The following equation is used to convert a simulated distilation (SD) in weight percent to an ASTM D886 distillation in volume percent ASTM D86= a(SD)"F GAR.) Where ‘a,b, = constants varying with percent of liquid sample distilled as given below. % Distilled a b € 0 6.01s4 0.7445 0.2879 10 42262 0.7044 0.2671 30 4.8882 o7m9 0.3450 50 24.1357 0.5425 07132 70 1.0835 0.9867 0.0486 90 1.0956 0.9834 0.0354 100 1.9073 0.9007 0.0625 ASTM DB6= observed ASTM D86 temperatures at 0+, 10-, 30-, 50-, 70-, 90+, and 100-volume percent points, in degrees Rankine. SD = simulated distillation temperatures at corresponding weight percent points, in degrees Rankine. F = parameter given by equation (3A3.1-2, F = 0.009524(5D 109%)" (SD Sos)?" Gas) Where: SD 10% = SD temperature at 10% point, degrees Rankine SD 50% = SD temperature at $0% point, degrees Rankine, Equations (3A3.1-1) and (3A3.1-2) ae also shown in Figures 3A3.2 and 343 3, respectively ‘At the bottom of Figure 33.2, the center portion is enlarged to more cleanly show the ‘relationship between parameters, Procedure Step 1: Obtain parameter F from equation (3A3.1-2) or Figure 33.3. Step 2: Use equation (3A3.1-1) with the appropriate constants as given below at each percentage point to obtain the ASTM distillation curve, Alternatively use Figure 33.2. 1987 att33.4 a2 COMMENTS ON PROCEDURE 943.1 Purpose “The purpose of this procedure is to predict an ASTM 86 distillation from a simulated distillation (ASTM D2887) at atmospheric pressure. The procedure is intended for both desk and computer use Limitations Equation 3A3.1-1 cannot be used reversibly to predict an SD distillation from an ASTM 186 distillation, Also this procedure should not be used outside the temperature ranges specified below: Simulated Distillation Weight % Distilled ‘Temperature Range, F 0 50-390 10 74442 30 93-493 50 11-545 % 7-581 90 179-655 100 207-762, Reliability Differences between the estimated and experimental ASTM D86 temperatures at various points ae given below. Data sets for 117 fractions were used to evaluate the accuracy of the procedure. Volume 9% Average Disilled Deviation, F 0 25 10 92 30 16 50 7 7 61 30 84 10 188 In addition, an evaluation of the two-step SD-ASTM-TBP method was made (Procedures 3AL.1 and 3A3.1). Differences between the estimated and experimental TBP temperatures ‘at various percent points are given below. Data sets for nine fractions were used to evaluate the accuracy of the procedure. Volume % Average Distilled Deviation, F 10 82 30 99 0 92 0 88 » 108 Literature Source This procedure was developed by M. R. Riazi, The Pennsylvania State University, Univer- sity Park, Pa., private communication (1985). Example Estimate the ASTM D&6 distillation curve of a petroleum fraction having the following simulated distillation (ASTM D2887) temperatures: Percent distilled coves O 10 3050 70 90 100 SD temperature, F 32 137 216 273 312. 383400 First, estimate parameter F from equation (33.1.2) F = 0,009524(137 + 460)!" (273 + 460) 77181987 3A3.1 (Alternately from Figure 3A3.3, F=0.78). Next, use equation (3A3.1-1) at each distillation point. ASTM D86 @ 0% = 6.0154(52 + 460)! (0.7778)°2" =582R 12F ASTM D86 @ 10% = 4.2262(137 + 460)°"™*(0.7778)"=" GAR =14F Similarly ASTM D86 temperatures at other points can be estimated. A complete predicted ‘ASTM curve follows. Volume % distilled «.....2.... Of 10 30) 00) 0) 190) 100) ASTM D86 temperature, F Predicted .. fers W221 2S 263 296 330 365 Experimental ia i Zi 258 22 3K 3m 313,-50 0 FIGURE 3A3.2 800 SIMULATED TO ASTM D86 7 50 50 DISTILLATION CONVERSION 100 AT ATMOSPHERIC PRESSURE 700 150 TECHNICAL DATA BOOK 6504 ‘ID JUNE 1986 7 ae Approved: TED 600 4 200 q 3 w 4 =250 & _ 550 S ¢ 300 = = 500 g - $ < 360 2 = 450 z we Ww 2 4 a 7 400 i 2 400 4 el 2 - q a 450 = * © 3504 9 a. 4 a 4 500 = 3005 = 9 - 4 E a 650 < < 250-4 7 600 & 200 650 150 700 100 4 750 50 800 oa 850 a4 1987303.3 009 4 ‘037111810 %0S LY SHNLVH3SdW3L NOLWLVITILSIG G3LVINWIS oos ooy ooe ooz oor a: NoIsuaANoD ereve au oan ipeetey pal Bune G xooe vive twamnons = a RZBY-NOLLYTIULSIO BAVIAWIS BOs 4 UBLaMVEVE noid so on se os se oe se 008 4 4aLaWVeVd B15, 1987PROCEDURE 344.1 INTERCONVERSION OF DISTILLATION DATA FOR PETROLEUM FRACTIONS AT ‘SUBATMOSPHERIC PRESSURES Discussion The following procedure is recommended to convert ASTM or TBP distillation data between subatmospheric pressures (usually 1, 10, 100 mm Hg) and between subatmospheric pressures and atmospheric pressure (760 mm Hg). Procedure A. Data at Subatmospheric Pressure ‘Step 1: Assume the Watson K of the petroleum fraction is 12, and convert the data using Procedure SA1.13, ‘Siep 2. Since the Watson K is set at 12, no Watson K correction is necessary, B. Data at Atmospheric Pressure : ‘Step 1: Ifthe specific gravity and mean average boiling point are known or can be caleu- lated, determine the Watson K from the defining equation (2-0.8). Otherwise assume K=i2. ‘Step 2: Follow Procedure SA1.13. 3A4.1 3173A41 COMMENTS ON PROCEDURE 344.1 Purpose "The purpose ofthis procedure is to convert petroleum fraction ASTM or TBP distillations from one pressure to another up to atmospheric pressure. This procedure is intended for both desk and computer use. Limitations. [Limitations are the same as given for Procedure SA1.13. Reliability Reliability isthe same as given for Procedure SA1.13. If the Watson K is taken to be 12, larger errors will result, especially for highly aromatic fractions. Example Consider a 31.4°API Saudi Arabian crude for which extensive TBP data are available. Four experimental TBP distillation data points are: Measured TBP Pressure, Volume APL ‘Temperature, F mom Hg. % Distilled Gravity 450 760 30 445 252 10 En 408 463 10 58 263 403 1 a 247 Interconvert these data to distillation temperatures at each of 1,10, and 760 mm Hg pressure. ‘Although it is not necessary in this case, assume K = 12 and read results directly from Figure 5A1.14b. The measured temperature at one pressure can be converted to each of the other two pressures, The results are given below: Volume % Distilled rrr C—O Pressure, mm He TBP Temperate, F 760 450" 42 742, 782 10 218 252" 463° 48 1 ut ns 3 403 * Experimental values. Each tabulation shows good consistency. In this case, note that the actual Watson K is calculable for the first point and could be used withthe full Procedure SA.13. For example, for the first point: K = (450+ 460)!/[141 SI(3L.5 + 44.5)] © 12.06 ‘The Watson K for the entire crude, assuming a MeABP of 617 Fis 11.8 and could be used as an estimate forall fractions distiled at subatmospheric pressure. 19871978 PROCEDURE 5A1.19 VAPOR PRESSURES OF PURE HYDROCARBONS AND NARROW-BOILING PETROLEUM FRACTIONS, Fig, SA1.14 and SAI.15 are useful for estimating the vapor pressures of pure hydrocarbons and narrow-boiling petoleum fractions when the eal properties or the aceniic factors are not knowa and cannot be estimated. If these properties are available Procedure 5A1 10 is recommended Procedure Step 1: Obtain the norma boiling point ofthe bygrocatbon from Chap. 1 and the Watton K from Chap. 2, Siep 2: Read a vapor pressure from Fig. SA1.14 using = f, where fs the norm boing point ‘nd v8 the normal boiling point corrected to K = 2 (both in degrees Fahtenbelt). For aaphihenes, olefins, acetylenes, and low-moleculat-weight (= Ca) paraffins it hot genetally benefit apply the ‘Watson K-correction, so the procedure is complete. For other hydrocatbons. proceed to Step 8 Sep 3: Using the vapor pressure from Step 2, obtain a K-correcion from Fig, SA115, Subtract this A (corrected with f muliplier for superatmospherie pressures) from the rue normal Boiling pot to get the corrected normal boiling point, Step 4: Repeat Steps 2 and 3 until the pressure used to estimate the K-corréction in Step 3 agrees hig desired mits with the value predicted in Step 2. In each repetition. the f from Step #8 ured Step 2 [Not To estimate a normal boiling point from a known vapor pressure, simply determin the 1 ftom Fig. SALI and add the K-correction from Fig. SA1-15,No tral andkerror approach i necessary This procedure may also be used with a digital computer. Fig. SAI.14 was generated from the following equations 300.538. ~ 6.761560 SEX ~ ODETTE 2663.129 x ~ 5.994296 logp* = for X > 0.0022 (p* <2.mm He) Garay toppt 2B 9X — 59982 (sans) for 0.0013 = X = 0.0022 (2 mim Hy = p* = 760 mm He) + = FIO X= GANPEN os «4.9053 (p* > 760 mH Salis tog pt = 2S A 6A io x < 0.0013 (pt > 760 mm Hg) (A139) Where » vapor pressure iam He Booman irs) 1'mm Hg and 30% focp" between 10-* and | aim Hg. Forp* < 10"* mm Hg ao experimental a ble and the elbiity of the method is unknown. The method is mot relable for vapor pressures neat atmospheric pressure. The method has not been tested with petroleum fraction data, Literature Sources Fig. SAL.14a-e and SAL.1S and equations (SA1.13-8) and (SAL.13-5) were adapted from ‘Maxwell and Bonnell, Vapor Pressure Charts for Petroleum Engineers, Esso Research and Engincerig Company, Linden, NJ (1955). Equations (5A1.13-1) through (SA113-3) were obtained from Exon Research ‘snd Engineering Company, Florham Park, NJ. private communication (1977), Fig SAL.14% is from Beerbower, A. and Zudkeviteh, D., “Predicting the Evaporation Behavior of Lubicants in the Space Environment,” Preprints, Division of Petroleum Chemisty, American (Chemical Society, Los Angeles Meeting, 8(2) €-99 (Ape 1963), Examples ‘A. Calealate the vapor pressure of 1 2,3,-tetrahydronaphthalene (tetraln) st 302 F From Chap. 1, the boiling point i 405.7'F, and from Chap. 2, the Watson K is 9.78. For the first rial, assume = 1p » 405.7 F. Using hist, and the desired temperature, 302 F, the fist estimate of the vapor pressure fs read fvom Fig. SAL.14a 28 0.20 atm, Ths Vapor presute (152 sum Hg) and 2 Watson K of 9.78 are used in Fig. SAIS to estimate the Watson K-eorrecuon, At = 4.0 F. The forthe second tral is 15 ~ (y ~ ) = 405.7 ~ 4.0 = 401.7 F Using the new the second tal vapor pressure is 0.21 atm (160 mm He) from Fig. SA1.14 From Fig: SA1.15, the new Watson K-coreston it 3.9 F; thus, the thd tial fs 408.7 — 3.9 = 4018. With f = 401.8 F, the estimated vapor pressure forthe third trial is read trom Fig. SA1.140 as 0.21 atm. This value is identical with the Second tial vapor pressure ths, the trial-and-error solution isSaustied ‘The estimated vapor pressure, 3.1 pin, agrees well with an experimental value of 3.13 psi BB. A petroleum fraction exhibits the following TBP disillaton curve at 10 mm Hg Distillation, percent by volume ..... fe 0 es ree | on, ‘Temperature, deg F 350 380425 S00 td Estimate the average normal boiling point ofthe 10. to 30-percent portion (the Watson K is 12.5) of the fraction, “The average boiling point at 10 mm Hg is 365 F. From Fig. $A1.14b, 15 = 628 F. From Fi SALIS.4~ = —24F. Therefore, the average agrmal boing point = #5 + Mp —tt) = 628 ~ CIS, 1978